CS235345B2 - Method of n-fluoralkylendioxyphenyl-n-benzoyl (thio)-ureas production - Google Patents

Description

The present invention provides novel N-fluoroelkylenedioxyphenyl-N'-benzoyl (thio) ureas and processes for their preparation.

It is already known that certain benzoyl ureas, such as N- (4-chlorophenyl) -N ^a - (2,6-difluorobenzoyl) urea, N- (4-trifluoromethoxyphenyl) -N '- (2-chlorobenzoyl) urea and N- (2,2,4,4-tetrafluoro-1,3-benzodloxin-6-yl) -N '- (2-chlorobenzoyl) urea, having insecticidal properties (vis [DE-O 8, 2 123 236, 2 601,780, 2,637,947 and 3,023 / 328).

We have now found new substituted N-fluoroalkylenedioxyphesyl-N ^from -benzoyl (thio) aureas of the formula I χ

CO-NH-C-NH (I)

in which

R * represents a hydrogen atom or a halogen atom,

R is halogen, C 1 -C 4 alkyl or C 1 -C 4 alkylthio; and

X is an oxygen or sulfur ethome,

23534 5/1, with the exception of the compound in which R represents a hydrogen atom, R represents a fluorine atom at the 2-position, X represents a sulfur atom and Y represents a hydrogen atom.

These compounds can be used as pest control agents, especially as insecticidal agents. Said insecticidal compositions and process for the preparation of the active compounds of the above general formula (1), comprising the treatment of the corresponding substituted beznoyl lso (thio) cyanates with 7-amino-2,2,3,3-tetrafluorobenzo-1,4-dioxanam, are the subject of our related Czechoslovakia. No. 235327.

Another object of the present invention is to provide a process for the preparation of the above general formula (1), characterized in that the substituted phy _co- nh _{2 of} said novel compounds are benzemides of the general formula (II) in which:

A ²

R ¹ e R ² have the abovementioned meaning, are reacted with fluoralkylendioxylenyliso (thio) -kyanéty formula III

(III) optionally using a diluent, and the resulting products of formula (I) are isolated.

A preferred alkyl group for R is methyl ethyl, especially methyl, and preferred alkylthio is methylthio.

X is preferably oxygen.

2

The symbols R and R may occupy any positions on the phenyl ring, in particular positions 2, 6,

2.5, 2.4 or 3.4, especially the 2.6, 2.4 or 2.5 positions, and most preferably the 2.6 position. If it means 12

R is a hydrogen atom, preferably R is 2,3 or 4, most preferably at position 2.

2

The halogen atoms R and R are preferably fluorine, chlorine and bromine atoms, in particular fluorine and chlorine.

Particularly suitable are those compounds of formula (I) wherein:

R ¹ represents hydrogen, fluorine, chlorine, thunder or iodine, preferably hydrogen, fluorine or chlorine

R ² represents a fluorine, chlorine, bromine or iodine atom or a methyl group, preferably fluorine or chlorine and

X is an oxygen or sulfur atom, preferably an oxygen atom,

2, with the exception of the compound in which R represents a hydrogen atom, R represents a fluorine atom in the position

2, X represents a sulfur atom and Y represents a hydrogen atom.

The positions of the R symbols correspond to what has been mentioned above for these symbols.

Particularly preferred are those compounds of formula I wherein:

R ¹ represents a hydrogen, fluorine or chlorine atom;

R represents a fluorine or chlorine atom;

X is a kink,

2 wherein the positions of the symbols R and R correspond to what has been mentioned above for these symbols.

If 2,6-fluorobenzamide and 3,4- (tetrafluoroethylenedioxy) phenyl isocyanate are used as starting materials in the process according to the invention, the reaction is described as follows:

The benzoic acid amides of formula II used as starting materials are known or can be obtained by conventional methods analogous to known procedures [see, for example, J. Org. Chem. JO, (1965), 4306-4307 and DE-As 1 2.5 144].

The other starting materials used for the fluoralkylenedioxyphenyliso (thio) cyanates of the formula (III) are also known or can be prepared by conventional methods analogous to known processes (cf. DE-OS 2 84 8 531).

The process for preparing the novel N-fluoroalkylenedioxyphenyl-N'-benzoyl (thio) ureas according to the invention is preferably carried out using diluents.

Suitable diluents are virtually all inert organic solvents, which include in particular aliphatic and aromatic or halogenated hydrocarbons such as pentane, hexane, heptane, cyclohexane, petroleum ether, petrol, ligroin, benzene, toluene, xylene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene, ethers such as diethyl and dibutyl ether, _from dimethyl glycol and dimethyl ether of diglycol, tetrahydrofuran and dioxane, ketones such as acetone, methyl ethyl ketone, methylisopropyl ketone and methyl isobutyl ketone, esters such as methyl acetate and ethyl acetate, nitrile and ethyl acetate, nitrile propionitrile, amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone, as well as dimethylsulfoxide, tetramethylenesulfone and hexamethylphosphoric triamide.

The reaction temperature can be varied within wide limits. In general, it is operated at a temperature between 20 and 180 ° C, preferably at a temperature of 60 to 120 ° C.

The process of the invention is generally carried out under normal pressure.

To practice the process of the invention, the starting materials are usually employed in equimolar amounts. The excess of some of the reaction components does not bring any significant advantages. The reaction is generally carried out in a suitable diluent and the reaction mixture is stirred at the desired reaction temperature for several hours. The resulting mixture is then allowed to cool and if the resulting product is sparingly soluble in the solvent used, the crystallized material is filtered off. Otherwise, isolation and, optionally, purification are carried out by conventional methods, for example by evaporation of the solvent (optionally under reduced pressure). Melting point, NMR spectrum and elemental analysis were used to characterize the products.

235345 4

The invention is illustrated by the following non-limiting examples.

Example 1

To 3.14 g (0.02 mol) of 2,6-difluorobenzemide in 30 ml of dry toluene was added 4.98 g (0.02 mol) of 2,2,3,3-tetrafluoro-7-isocyanetobenzo-2,4-dioxene. (n = 0 = 1.4661). The reaction mixture was stirred at 120 ° C for 16 hours, cooled to 20 ° C, and the precipitated product was filtered off with suction and washed with petroleum ether. 7.5 g of the desired product are obtained (% 2% of theory);

The compounds shown in the following tables are prepared in an analogous manner.

Example _B 1 ' _R 2' number Melting point (° C)

2 Cl Cl 0 202 3 Cl F 0 197 4 H Br 0 199 5 H Cl 0 198 6 H F 0 169 7 H ^C 2 »5 0 137 8 H SCH ₃ 0 197 9 F F WITH 189 10 Cl F WITH 203 1 1 H ’ Br WITH 172 12 H ch ₃ with 154 13 Cl Cl with 208

Table

F

example number R ¹ R ² X temperature 14 2-C1 4-F 0 157 15 Dec 2-G1 5-F 0 182 16 H 3-C1 0 194 17 H 4-C1 0 224 18 3-C1 4-C1 0 197

OBJECT OF THE INVENTION

Claims (1)

A process for the preparation of N-fluoroalkylenedioxyphenyl-N'-benzoyl (thio) ureas of the formula I X in which (AND) F R ¹ represents a hydrogen atom or a halogen atom, R ² is a halogen atom, an alkyl group having 1 to 4 carbon atoms, and C 1 -C 4 or alkylthio- X means an oxygen or sulfur atom, except the compound wherein R ¹ is hydrogen, 2 R represents a fluorine atom in a semi- of 2 and X is a sulfur atom, characterized in that it is a substituted benzemide of formula II ' - CO-NH ₂ (II) in which R ^z 1 2 R and R are as defined above, reacted with fluoroalkylenedioxyphenyliso (thio) cyanates of formula III, optionally in the presence of a diluent, at a temperature of 20 to 180 ° C, preferably 60 to 120 ° C.